Photographic silver halide color material utilizing benzoylacetamide color couplers

ABSTRACT

Photographic materials are described comprising a lightsensitive silver halide emulsion layer and a benzoylacetamide color coupler capable of forming a yellow azomethine dye by reaction with an oxidized aromatic primary amino developing agent in which the benzoyl part of the color coupler contains at least one substituent of the formula : RCF2Qwherein : R is hydrogen, fluorine or polyhaloalkyl, and Q is oxygen, sulphur or sulphonyl. These color couplers in light-sensitive silver halide emulsions provide photographic materials having improved light stability.

United States Patent Verbrugghe et al.

[ 1 May2,1972

[54] PHOTOGRAPHIC SILVER HALIDE COLOR MATERIAL UTILIZINGBENZOYLACETAMIDE COLOR COUPLERS Inventors: Marcel Hendrik Verbrugghe,Wilrijk; Arthur Henri De Cat, Mortsel, both of Belgium Int. Cl. ..G03c7/00, G03c l/40 Field of Search ..96/55, 100

References Cited UNITED STATES PATENTS Salminen et a1. ..96/ 100Hoffstadt ..96/ l 00 Verbrugghe et a1. ..96/100 Primary Examiner-J.Travis Brown AttorneyAlfred W. Breiner [57] ABSTRACT Photographicmaterials are described comprising a light-sensitive silver halideemulsion layer and a benzoylacetamide color coupler capable of forming ayellow azomethine dye by reaction with an oxidized aromatic primaryamino developing agent in which the benzoyl part of the color couplercontains 7 at least one substituent of the formula:

RCG Q wherein:

Ris hydrogen, fluorine or polyhaloalkyl, and

Q is oxygen, sulphur or sulphonyl. These color couplers inlight-sensitive silver halide emulsions provide photographic materialshaving improved light stability.

8 Claims, No Drawings PHOTOGRAPHIC SILVER HALIDE COLOR MATERIALUTILIZING BENZOYLACETAMIDE COLOR COUPLERS This invention relates to theproduction of photographic color images, to yellow forming colorcouplers used therein and to photographic materials containing suchcolor couplers.

it is known that for the production of a photographic color image in alight-sensitive silver halide layer, the exposed silver halide isdeveloped to a silver image by means of an aromatic primary aminocompound in the presence of a color coupler which reacts with theoxidized developing substance to form a dyestuff on the areascorresponding to the silver image.

In the subtractive three-color photography a light-sensitivephotographic color material is used containing a red-sensitized, agreen-sensitized and a blue-sensitive silver halide emulsion layerwherein on color development, by the use of appropriate color couplers,a cyan, magenta and yellow dyestuff image are formed respectively.

One of the basic difficulties confronting color photography concerns thestability of the dyes making up the colored photographic images againstlight, heat and humidity. Although color photography has undergone muchimprovement since the appearance of the use of coupler compounds for theformation of colored images, greater dye stability is still needed andsought after.

According to the present invention there are provided novelbenzoylacetamide color couplers comprising in the benzoyl part at leastone substituent corresponding to the formula RCF Q- wherein Q stands foroxygen, sulphur, or sulphonyl and R stands for hydrogen, fluorine orpoly-halo-alkyl such as -CHF -CHFC1, -Cl-lFBr, -CFCl -CCl -CHF-CF etc.

More particularly, in accordance with the present invention there areprovided novel yellow forming color couplers corresponding to thefollowing generalformula wherein Q and R have the samesigniflcance asabove,

X stands for a hydrogen atom or a substituent that exhibits twoequivalent character on color development e.g. a halogen atom, a -S-Rgroup wherein R, stands for alkyl including substituted alkyl, arylincluding substituted aryl or a heterocycle including a substitutedheterocycle; etc. or an O-R group wherein R stands for alkyl includingsubstituted alkyl, aryl including substituted aryl, or acyl includingsubstituted acyl such as acetyl and benzoyl, Z stands for hydrogen, thegroup RCF Q- wherein R and Q have the same significance as above or asubstituent e.g. alkyl such as methyl, alkoxy such as methoxy, halogensuch as chlorine, and dialkylamino such as dimethylamino, and Arepresents an aromatic nucleus such as phenyl and naphthyl including asubstituted aromatic nucleus or a heterocyclic nucleus such as thiazoleand pyridine, including a substituted heterocyclic nucleus, said colorcouplers preferably being fast to diffusion in photographic colloidlayers by the presence in the amide part of the molecule of a radical,which is directly linked to the group A or through a substituentthereof, rendering the compound fast to diffusion and corresponding tothe formula -Y-D wherein D stands for an acyclic aliphatic hydrocarbonresidue with from 5 to 20 carbon atoms and Y stands for a chemical bond,oxygen, sulphur, sulphonyl, N(alkyl), CONH-, NHCO, N(R )SO or S0 N(Rwith R H or alkyl.

The aryl or heterocyclicgroup represented by A comprising a ballastinggroup rendering the color couplers less liable to diffuse from aphotographic colloid layer in which it is incorporated may be any ofthose customarily present in the amide part of the benzoyl-acetamidecolor couplers. Numerous examples of color couplers carrying such aryland heterocyclic groups, some of which comprise in addition to the saidballasting group substituents favorably influencing --the physical,

the general fonnula wherein:

Y-D has the same significance as above, and

Z stands for a hydrogen atom or any substituent that favorablyinfluences the physical, spectral or sensitometric properties of themolecule e.g. alkyl includingsubstituted alkyl such as carboxyalkyl,sulphoalkyl, aryl including substituted aryl, halogen such as chlorine,a water-solubilizing group such as sulpho or carboxyl in acid or saltform, a fluorosulfphonyl group, an alkoxy-carbonyl group such ascarbethoxy, a sulpharnoyl group including a substituted sulpharnoylgroup such as diethylsulphamoyl, phenylsulphamoyl, an alkylsuphonylgroup such as methylsulphonyl, an alkoxy group such as methoxy, analkylthio group such as methylthio, an aryloxy group including asubstituted aryloxy group, an arylthio group including a substitutedarylthio group, or the group wherein each of R and R stands for alkyl,aryl, aralkyl or together represent the atoms necessary to form amopholine nucleus or piperidine nucleus.

The color couplers of the present invention are distinguished from allknown benzoylacetamide color couplers by having attached to the benzoylgroup at least one substituent of the formula RCF Q- wherein R and Qhave thesignificance given above. The colorcouplers of the presentinvention have useful properties not shared by couplers ofthe samestructure except that they do not contain said RCF Q group in thebenzoyl part of the molecule. One such useful property is that the dyesproduced from the color couplers of the present invention have amarkedly improved light-stability as compared with dyes similarlyproduced from the known benzoylacetamide color couplers.

Apart from manifesting a high stability against light, the dyes formedon color development from the color couplers of the present inventionpossess favorable spectral properties and a high degree of resistanceunder conditions of high humidity and heat.

The following compounds are representative color couplers of the presentinvention. However, it is tobe understood that the invention is notlimited to these specific couplers.

1. (1) 0 won l Cl (I)C r.ll3,1

-c 0 01m: ONII C O OH 2. (|)C16H3a 111w OQ-o 0 cute ONII 1 COOH 3.OCFzCIIFCl {00mm 11300-- -C0ClI2C0NII' SOuNlL V inc o c cmoomr 8. S CFzCHF Cl 9. S OZCHFQ COCH1OONH 10. O C F FgI-I 11. O C FzC Cla C wHsa SOzN 0 0 01120 ONII- s 020181133 0 0 01120 ONILQQ-IJMHM 12. O C FzC F Ch(11511113 o0cmcom1 $03K 13. ?CI6II33 FsC0COCHzCONH- 14. FJCIIFCFzCO-Q-CO OHzCONH- V(|)CH:

CI-IzCIHCHDaCH;

s O N omcmcmiscm 15. OCFzCHFCl 00151133 As will be illustrated in thepreparation hereinafter the yellow-forming benzoylacetamide colorcouplers according to the present invention can be prepared according tothe methods known in the art of preparing benzoyl-acetamide colorcouplers by condensing the appropriately substituted benzoylacetic acidesters with aromatic or heterocyclic amines containing a diffusion-fastmaking group.

The preparation of the amino compounds containing adiffusion-fast-making group can be prepared analogously to thepreparation technique illustrated hereinafter. A detailed description ofthe preparation of all aromatic and heterocyclic amino compoundssuitable for being condensed with the benzoylacetic acid esters is notdeemed necessary since the preparation will not cause difficulties tothose skilled in the art of preparative organic chemistry. A wholeseries of aromatic and heterocyclic amines which comprise a grouprendering the molecule non-migratory and which are suitable for beingcondensed with the benzoyl acetic acid esters substituted with the groupRCF Q, Q and R having the same significance as above, in order to formcolor couplers according to the present invention can be found in U. K.Pat. Nos. 939,030, 983,648, 1,099,418 and 1,104,729 and in US. Pat. Nos.3,138,604, 3,369,899, 3,393,040 and 3,393,041.

Examples of benzoylacetic acid esters suitable for being condensed witharomatic or heterocyclic amines to form color couplers according to thepresent invention are 0- and p-(l,l,2-trifluoro-2-chloroethoxy)benzoylacetic acid ethyl ester,

o-( 1, l ,2-trifluoro-2-chloroethylthio)-benzoylacetic acid ethyl ester,p-difluoromethyloxybenzoylacetic; acid ethyl ester, 2,2-di(1,1,2-trifluoro-2-chloroethoxy)-benzoylacetic acid ethyl ester,

2-( l 1 ,2-triflu0r0-2-chloroethoxy)-4-methoxy-benzoyl acetic acid ethylester,

m-difluoromethylsulphonylbenzoylacetic acid ethyl ester, 0- and m-( 1,1,-difluoro-2,2,2atrichloroethoxy)-benzoyl-acetic acid ethyl ester, 4o-'( l,1,2,2-tetrafluoroethoxy) benzoylacetic acid ethyl ester,p-trifluoromethoxybenzoylacetic acid ethyl ester, p-( 1,1,2-trifluoro-Z-bromoethoxy)-benzoylacetic acid ethyl ester, o-( l l,2-trifluoro-2,2dichloroethoxy)-benzoylacetic ethyl ester, andp-(1,l,2,3,3,3,-hexafluoropropoxy)-benzoylacetic acid ethyl ester. I

acid

PREPARATION. l 1

a. o-(1,l,2-trifluoro-2-chloroethoxy)-benzoylacetic acid ethyl ester.

27.3 g. of o-(l,l,2-trifluoro-2-chloroethoxy)-benzoyl chloride(Bull.Soc.Chim.Fr. 1957, 821) were added with stirring to a suspensionof 30.4 g. of the sodium salt of ethylacetoacetate in 50 ml. ofdichloromethane. After having been stirred for three hours the mixturewas acidified with hydrochloric acid. The dichloromethane layer wasseparated, washed with water until acid free and concentrated byevaporation. The remainting oily residue was added to a solution of 4 g.of a sodium hydroxide, 4 m1 of ammonium hydroxide and 13.3 g. ofammonium chloride in 60 ml. of water. The mixture was stirred for threehours at 40 C. whereupon the solution was extracted withdichloromethane. The extract was washed with water, dried andconcentrated by evaporation. The residue was distilled yielding acolorless oil with boiling point: l35-l36 C./1 mm.

b. 3-nitro-4-hexadecyloxybenzoic acid 39.4 g. of3-nitro-4-hydroxy-benzoic acid methyl ester, 13.2 g. of potassiumhydroxide and 61 g. of hexadecylbromide where refluxed for five hours.The ester group was hydrolized by boiling with g. of potassium hydroxidein 100 m1. of water. The reaction mixture was poured into diluted acidyielding a light-brown grainy product. This product was recrystallizedfrom ethanol.

Melting point: 96-98 C.

c. 3-amino-4-hexadecyloxybenzoic acid 40.7 g. of3-nitro-4-hexadecyloxybenzoic acid in 170 ml. of ethylene glycolmonomethyl ether were hydro-genated at 80 C. using Raney Nickel ascatalyst and a hydrogen pressure of 1,500 p.s.i. A crystalline productvarying from white to lightbrown was obtained.

Melting point 99100 C. d. o-( 1 l,2-trifluoro-2-chloroethoxy)-benzoy1-(2-hexadecyloxy-S '-carboxy)acetanilide 32.5 g. of the above B-ketoester and 37.7 g. of the aboveamino compound were refluxed in 100 ml. of xylene. The mixture of xyleneand ethanol formed was gradually distilled off in about 1 h. Uponcooling a crystalline precipitate formed which was filtered off andwashed with hexane.

Melting point: 140 C.

PREPARATION 2 a. p-difluoromethoxybenzoic acid.

31.6 g. of p-tolyl difluoromethyl ether (Miller, Thanassi, J.Org.Chem.25, 1960, p. 2010) were oxidized by means of 158 g. of potassiumpermanganate in 1,000 ml. of water at boiling temperature.

Melting point: 171 C.

b. pdifluoromethoxybenzoyl chloride.

37.5 g. of p-difluoromethoxybenzoic acid prepared as described abovewere boiled with 45 ml. of thionyl chloride. The excess of thionylchloride was distilled off yielding a colorless liquid with boilingpoint: 72 C./5 mm.

c. p-difluoromethoxybenzoylacetic acid ethyl ester.

This compound was prepared according to the method described inpreparation La) starting from 20.65 g. of pdifluoromethoxy-benzoylchloride. A light yellow oil with boiling point 146 C /1 mm wasobtained. d. p-difluorornethoxybenzoyl-( 2 '-hexadecyloxy-5'-carboxy)-acetanilide This compound was prepared in an analogous way asthe compound of preparation l.d) from 25.8 g. of the above aketoesterand 37.7 g. of the amino compound of preparation l.c). The crude productwas recrystallized from isopropanol.

Melting point: 155C.

PREPARATION 3 a. o-( 1,1,2-trifluoro-2-chloroethoxy)-p-methoxybenzoicacid methyl ester o-( l ,1,2-trifluoro-2-chloroethoxy)-p-methoxybenzoicacid methyl ester was prepared according to the method of Lichtenberger(Bull.S0c.Chim.Fr. 1962, p. 259) starting from 72.8 g. of2-hydroxy-4-methoxybenzoic acid methyl ester (Herzig Monatsh.f.Chem. 24(1903) p. 1.887). A colorless oil was obtained having a boiling point of136-l40C/ l .5 mm.

b. o-( l l ,2-trifluoro-2-chloroethoxy)-p-methoxybenzoic acid 60 g. ofthe foregoing compound were hydrolized by boiling with ml. of 5 N sodiumhydroxide in ml. of methanol. The reaction mixture was poured intodiluted acid. A white crystalline product with melting point 1 10 C. wasobtained.

c. o-( 1,1,2-trifluoro-2-chloroethoxy)-p-methoxybenzoyl chloride.

This compound was prepared according to the method described inpreparation 2.b) starting from 56.9 g. of the corresponding acid. Acolorless oil with boiling point 176 C./ 18 mm. was obtained. d. o-(1,1,2-trifluoro-2-ch1oroethoxy)-pmethoxybenzoyl-acetic acid ethyl ester.

This compound was prepared according to the method described inpreparation 1.a) starting from 30.3 g. of the acid chloride. A lightyellow liquid with boiling point 180 C./O.7 mm. was obtained. e.0-(1,1,2-trifluoro-2-chloroethoxy)-pmethoxybenzoyl-( 2 '-hexadecyloxy-5-fluorosulphonyl)- acetanilide.

35.5 g. of the above a-ketoester and 41.5 g. of 3-amino-4-hexadecyloxybenzene sulphofluoride (prepared as described in UnitedKingdom Patent Specification 983,648) were allowedto react according tothe method described in preparation l.d). A white crystalline productwith melting point 85 C. was obtained after recrystallization fromacetonitrile. f. o-1,1,2trifluoro-2-chloroethoxy)-p-methoxybenzoyl-(2'-hexadecyloxy-S-sulpho)-acetanilide potassium salt.

7.23 g. of the above sulphofluoride in 40 ml of acetone were refluxedwhile stirring with 6 ml of 5 N potassium hydroxide. 'After having beenrefluxed for 30 minutes the reaction mixture was acidified with aceticacid. Upon cooling a white crystalline precipitate formed.

PREPARATION 4 a. o,p-di(1,l,2-trifluoro-2- chloroethoxy )benzoic acidmethyl ester o,p-di( 1,l,2-trifluoro-2-chloroethoxy)-benzoic acid methylester was prepared according to the method described in preparation 3.a)starting from 67.2 g. of dihydroxy benzoic acid methyl ester. Acolorless oil with boiling point 16l162 C/5 mm was obtained. b.o,p-di(1,1,2-trifluoro-2- chloroethoxy)benzoic acid was prepared asdescribed in preparation 3.b) starting from 80 g of the above methylester. A white crystalline product with melting point 70 C. wasobtained. c. o,p-di( 1, l ,2-trifluoro-2-chloroethoxy )benzoyl chloridewas prepared as described in preparation 2.b) starting from 77.4 g ofthe corresponding acid. A light yellow oil with boiling point C/ 19 mmwas obtained. d. o,p-di( 1,1,2-trifluoro-Z-chloroethoxy)benzoylaceticacid ethyl ester was prepared asdescribed in preparation 1.a) starting from 40.6 of the correspondingacid chloride. A yellow oil with boiling point 182 C./0.4 mm wasobtained. e. o,p-di( 1,1,2-trifluoro- 2-chloroethoxy( benzoyl-( 2-hexadecyloxy-5 -fluorosulphonylacetanilide 45.7 g. of the aboveB-ketoester and 41.5 g of 3- amino-4-hexadecyloxy-benzene sulphofluoride were allowed to react according to the method described inpreparation l.d). A white crystalline product with melting point 122 C.was obtained. f. o,p-di( l,1,2-trifluoro-2-chloroethoxy)benzoyl-( 2'-hexadecyloxy-5 '-sulpho )acetanilide potassium salt was preparedaccording to the method described in preparation 3.f) starting from 8.26g. of the sulphofluoride compound. After recrystallization from amixture of water and methanol a white crystalline product was obtained.

PREPARATION 5 acid This compound was prepared according to the methoddescribed in preparation l.d) starting from 32.5 g. of the above[3-ketoester and 27.7 g. of o-dodecyloxyaniline. A white crystallineproduct with melting point 116 C. was obtained after recrystallizationfrom methanol.

PREPARATION 6 a. o-( 1,1,1-trifluoro-2- chloroethylthio)benzoylaceticacid ethyl ester.

This compound was prepared according to the method described inpreparation 3.b), c) and d) starting from 57 g. of o-( l, l,2-trifluoro-2-chloroethylthio)benzoic acid methyl ester (Lichtenberger,Bull.Soc.Chim.Fr. 1962, p. 258). A light yellow oil with boiling point182 C./0.4 mm. was obtained.

b. o-( 1 ,1 ,2-trifluoro-2-chloroethylthio)benzoyl-(2'-hexadecyloxy-S-carboxy)-acetanilide.

This compound was prepared according to the method described inpreparation l.d) starting from 34 g. of the B- ketoester described instep a) and 37.6 g. of 3-amino-4-hexadecyloxybenzoic acid. A whitecrystalline product with melting point 165 C. was obtained.

PREPARATION 7 o-( 1 l ,2-trifluoro-2-chloroethoxy)-p-methoxybenzoyl-[2'-chloro-S-(N-methyl-N-hexadecylsulphamoyl)]acetanilide was preparedaccording to the method described in preparation l.d) starting from 35.5g. of o-(l,l,2-trifluoro-2- chloroethoxy)-p-methoxybenzoylacetic acidethyl ester and 44.5 g. of 2-chloro-5-N-methyl-N-hexadecylsulphamoyl)aniline (prepared as described in UK. Pat. specification No. 1,104,729).A white crystalline product with melting point 86C was obtained.

PREPARATION 8 2- o-(l,1,2-trifluoro-2-chloroethylthio)benzoylacetamido]-4-p-methoxyphenyl-5-tetradecylthiazolewas prepared according to the method described in preparation l.d)starting from 34 g. of o-(1,l,2-trifluoro-2-chloroethylthio)benzoylacetic acid ethyl ester and 40.2 g. of2-amino-4-p-methoxyphenyl-S-tetradecylthiazole (prepared as described inU.S. Pat. specification No. 3,393,041). The reaction mixture was takenup in acetonitrile and the solution was cooled to room temperaturewhereby a light yellow oil separated. v

The yellow color formers according to the present invention are of thenon-ditfusible type i.e., they comprise in their molecule an organicradical sufficiently large for preventing the color coupler of wanderingfrom the colloid layer, in which the coupler, is incorporated, toanother colloid layer.

For preparing a usable photographic multilayer color material thenon-diffusing color couplers for each color separation image are usuallyincorporated into the coating compositions of the differently sensitizedsilver halide emulsion layers. However, the non-diffusing color couplersmay also be added to the coating compositions of non-light-sensitivecolloid layers which are in water-permeable relationship with thelight-sensitive silver halide emulsion layers.

During the preparation of the light-sensitive color material thenon-migratory yellow forming color couplers according to the abovegeneral formulae can be incorporated in the coating composition of thesilver halide emulsion layers or other colloid layers in water-permeablerelationship therewith according to any technique known by those skilledin the art for incorporating photographic ingredients, more particularlycolor couplers, into colloid compositions. For instance, thewatersoluble color couplers i.e., those containing one or morewater-solubilizing groups such as sulpho or carboxyl groups (in acid orsalt form) can be incorporated into the coating composition of the layerin question from an aqueous solution and the water-insoluble orinsufficiently water-soluble color couplers from a solution in theappropriate water-miscible or water-immiscible high-boiling orlow-boiling organic solvents or mixtures. thereof whereupon the solutionobtained is dispersed, occasionally in the presence of a wetting ordispersing agent, in a hydrophilic colloid composition forming orforming part of the binding agent of the colloid layer. The hydrophiliccolloid composition may of course'comprise in addition to the colloidcarrier all other sorts of ingredients. The water-insoluble colorcouplers carrying fluorosulphonyl groups or carboxylic acid ester groupssuch as ethoxycarbonyl groups can also be converted by alkalinehydrolysis (e.g., as described in U.K. Pat. specification No. 939,030)in the corresponding sulphonic acids or carboxylic acids respectivelywhich in their turn can be incorporated in hydrophilic colloidcompositions in the form of their alkali salts from aqueous solutions.

The solution of said color coupler need not necessarily be dispersed ordissolved directly in the coating composition of the silver halideemulsion layer or other water-permeable layer. Said solution mayadvantageously be first dispersed or dissolved in an aqueousnon-light-sensitive hydrophilic colloid solution whereupon the resultantmixture, after the occasional removal of the organic solvents employed,is intimately mixed with the said coating composition of thelight-sensitive silver halide emulsion layer or other water-permeablelayer just before coating. For more details about particularly suitabledispersing techniques that can be employed for incorporating the colorcouplers of the invention into a hydrophilic colloid layer of aphotographic material there can be referred to U.K. Pat. specificationNos. 791,219, 1,098,594, 1,099,414, 1,099,415, 1,099,416 and 1,099,417,French Pat. specification Nos. 1,555,663, Belgian Pat. specification No.722,026 and to U.S. Pat. No. 2,304,940.

The couplers according to the invention may be used in conjunction withvarious kinds of photographic emulsions. Various silver salts may beused as the sensitive salt such as silver bromide, silver iodide, silverchloride or mixed silver halides such as silver chlorobromide, silverbromoiodide and silver chlorobromoiodide. The couplers can be used inemulsions of the mixed packet type as described in U.S. Pat. No.2,698,794 or emulsions of the mixed grain type as described in U.S. Pat.No. 2,592,243. The color couplers can be used with emulsions whereinlatent images are formed predominantly on the surface of the silverhalide crystal; or with emulsions wherein latent images are formedpredominantly inside the silver halide crystal.

The hydrophilic colloid used as the vehicle for the silver halide maybe, for example, gelatin, colloidal albumin, zein, casein, a cellulosederivative, a synthetic hydrophilic colloid such as polyvinyl alcohol,poly-N-vinyl pyrrolidone, etc. If desired, compatible mixtures of two ormore of these colloids may be employed for dispersing the silver halide.

The light-sensitive silver halide emulsions of use in the preparation ofa photographic material according to the present invention may bechemically as well as optically sensitized. They may be chemicallysensitized by effecting the ripening in the presence of small amounts ofsulphur containing compounds such as allyl thiocyanate, allyl thiourea,sodium thiosulphate, etc. The emulsions may also be sensitized by meansof reductors for instance tin compounds as described in French Pat. No.1,146,955 and in Belgian Pat. No. 568,687, imino-amino methane sulphinicacid compounds as described in U.I(. Pat. No. 789,823 and small amountsof noble metal compounds such as gold, platinum, palladium, iridium,ruthenium and rhodium compounds. They may be optically sensitized bymeans of cyanine and merocyanine dyes.

The said emulsions may also comprise compounds which sensitize theemulsions by development acceleration for example compounds of thepolyoxyalkylene type such as alkylene oxide condensation products asdescribed among others U.S. Pat. Nos. 2,531,832, 2,533,990, 3,210,191and 3,158,484, in U.K. Pat. Nos. 920,637 and 991,608 and in Belgian Pat.Nos. 648,710 and onium derivatives of amino-N-oxides as described inU.I(. Pat. No. 1,121,696.

Further, the emulsions may comprise stabilizers e.g., heterocyclicnitrogen-containing thioxo compounds such as benzothiazoline-Z-thioneand 1-phenyl-2-tetrazoline-5thione and compounds of thehydroxytriazolopyrimidine type. They can also be stabilized with mercurycompounds such as the mercury compounds described in Belgian Pat. Nos.524,121, 677,337 and 707,386 and in US. Pat. No. 3,179,520.

The light-sensitive emulsions may also comprise all other kinds ofingredients such as plasticizers, hardening agents, wetting agents, etc.

The non-diffusing yellow color formers described in the presentinvention are usually incorporated into a blue-sensitive silver halideemulsion for forming one of the differently sensitized silver halideemulsion layers of a photographic multilayer color material. Suchphotographic multilayer color material usually comprises a support, ared-sensitized silver halide emulsion layer with a cyan color former, agreen-sensitized silver halide emulsion layer with a magenta colorformer and a blue-sensitive silver halide emulsion layer with a yellowcolor former.

The emulsions can be coated on a wide variety of photographic emulsionsupports. Typical supports include cellulose ester film, polyvinylacetalfilm, polystyrene film, polyethylene terephthalate film and relatedfilms or resinous materials, as well as paper and glass.

For the production of photographic color images according to the presentinvention an exposed silver halide emulsion layer is developed with anaromatic primary amino developing substance in the presence of a colorcoupler according to the present invention. All color developing agentscapable of forming azomethine dyes can be utilized as developers.Suitable developing agents are aromatic compounds such as pphenylenediamine and derivatives for example N,N-dialkyl-pphenylene diamines suchas N,N-diethyl-p-phenylene diamine,N,N-dialkyl-N-sulphomethyl-p-phenylene diamines, andN,N-dialkyl-N-carboxymethyl-p-phenylene diamines.

The following examples illustrates the present invention.

EXAMPLE 1 '1 17 g. of a blue-sensitive silver bromoiodide emulsion (2.3mole percent of iodide) which comprises per kg 73.4 g. of gelatin and anamount of silver halide equivalent to 47 g. of silver nitrate, arediluted with 192.5 g. ofa 7.5 percent aqueous solution of gelatin and100 g. of distilled water. To the emulsion obtained is added a solutionof color coupler l of the above list of color couplers prepared bydissolving at55 C.

0.006 mole of the color coupler in 54 ml of distilled water, 6 ml. of 2N sodium hydroxide and 18 ml. of ethanol. After neutralization andaddition of the common additives such as stabilizers, wetting agents,and hardeners the necessary amount of distilled water to obtain 575 g.of emulsion is added whereupon the emulsion is coated on a cellulosetriacetate support pro rata of 150 g. per sq.m. The emulsion layer isdried and overcoated with a gelatin antistress layer.

After drying, the material formed is exposed for l/20 sec. through acontinuous wedge with constant 0.30 and then developed for 8 min. at 20C. in a developing bath of the following composition:

N:N-dicthyl-p-phenylene diamine sulphate 2.75 g hydroxylamine sulphate1.2 g sodium hexametaphosphate 4 g anhydrous sodium sulphite 2 ganhydrous potassium carbonate 75 g potassium bromide 2.5 g water to make1 liter borax 20 g anhydrous potassium bromide 15 g anhydrous sodiumbisulphate 4.2 g potassium hexacyanoferrateflll) 100 g water to make 1liter After bleaching, the material is rinsed with water for 5 min. andfixed in an aqueous solution of 200 g. of sodium thiosulphate per liter.

After a final rinsing for 15 min. the material is dried.

A yellow colored wedge image is obtained having an absorption maximum of436 mm.

EXAMPLES 2 and 3 Example 1 is repeated with the difference that colorcoupler l is replaced by 0.006 mole of color couplers 3 and 6.

Yellow colored wedge images are obtained both having absorption maximaof 432 nm.

EXAMPLE 4 l 17 g. of a blue-sensitive silver bromo-iodide emulsion (2.3mole percent of iodide) containing per kg 73.4 g. of gelatin and anamount of silver halide equivalent to 47 g. of silver nitrate are meltedand diluted with 192.5 g. of a 7.5 percent aqueous solution of gelatinand g. of distilled water. To theemulsion obtained is added a gelatingel comprising a dispersion of color coupler 5 prepared by admixing bymeans of an ultrasonic wave generator a solution of 0.006 mole of saidcolor coupler in a mixture of 14 ml. of ethyl acetate, 1.5 ml. oftricresyl-phosphate and 0.75 ml. of dibutylphthalate with 100 ml. of a 5percent solution of gelatin and removing the ethyl acetate byevaporation under reduced pressure. After neutralization and addition ofthe usual additives such as hardeners, wetting agents, and stabilizersthe necessary amount of distilled water to obtain 575 g. of emulsion isadded whereupon the emulsion is coated on a cellulose triacetate supportpro rata of g. per sq.m. The emulsion layer is dried and overcoated witha gelatin antistress layer.

Exposure and processing occurs as described in Example 1.

A yellow colored wedge image having an absorption maximum of 440 nm. isobtained.

EXAMPLES 5 and 6 Example 4 is repeated with the difference that colorcoupler 5 is replaced by 0.006 mole of color couplers 7 and 8.

Yellow colored wedge images are obtained having absorption maxima of 452nm. and 470 nm. respectively.

WE CLAIM 1. Photographic material comprising a light-sensitive silverhalide emulsion layer and a benzoylacetamide color coupler capable offorming a yellow azomethine dye by reaction with an oxidized aromaticprimary amino developing agent, wherein said color coupler correspondsto the following general formula:

wherein: R stands for hydrogen, fluorine or polyhaloalkyl, Q stands foroxygen, sulphur or sulphonyl, X stands for hydrogen or a substituentthat exhibits twoequivalent character on color development selected fromthe group consisting of a halogen atom, a -S-R group wherein R standsfor alkyl, aryl, and a heterocycle; or an O-R group wherein R stands foralkyl, aryl, and acyl, A stands for a member selected from the groupconsisting of a 6-carbon mononuclear aryl group, a IO-carbon dinucleararyl group, a thiazolyl group, and pyridyl group, and Z stands forhydrogen, the group RCF O- wherein R and Q have the same significance asabove, alkyl, alkoxy, halogen, or dialkylamino.

2. A photographic material according to claim 1, wherein 1 said colorcoupler is fast to diffusion in photographic colloid layers by thepresence in the amide part of its molecule of a group, which is directlylinked to the group A or through a wherein 1 Y stands for a chemicalbond, oxygen, sulphur, sulphonyl, -N(alkyl)-, -CONH-, -NHCO-, -N(R ,)SOand -SO N(R wherein R =H or alkyl,

D stands for an acyclic aliphatic hydrocarbon residue with from 5 to 20carbon atoms,

Z stands for hydrogen, an alkyl group, an aryl group, a halogen atom, asulpho or carboxyl group in acid or salt form, a fluorosulphonyl group,an alkoxycarbonyl group, a sulphamoyl group, an alkylsulphonyl group, analkoxy group, an alkylthio group, an aryloxy group, an arylthio group orthe group or piperidine nucleus.-

5. Photographic multilayer color material comprising in one of thelight-sensitive silver halide emulsion layers or in a nonlight-sensitivewater-permeable colloid layer in water-permeable relationship with thelight-sensitive silver halide emulsion layer a color coupler accordingto claim 1.

6. Photographic multilayer color material according to claim 5,comprising three silver halide emulsion layers which are differentlyoptically sensitized, wherein the bluesensitive silver halide emulsionlayer or a non-light-sensitive colloid layer in water-permeablerelationship therewith incorporates the said color coupler.

7. Process for the production of a photographic color image bydevelopment of a photographic element containing imagewise exposedsilver halide with the aid of an aromatic primary amino developingagent, which by reduction of the exposed silver halide is converted intoits oxidized form and as such forms a yellow azomethine dye by reactionwith a color coupler according to claim 1.

8. Process according to claim 7, wherein said color coupler is presentin a blue-sensitive silver halide emulsion layer or other colloid layerin water-permeable relationship therewith of the said photographicelement.

2. A photographic material according to claim 1, wherein said colorcoupler is fast to diffusion in photographic colloid layers by thepresence in the amide part of its molecule of a group, which is directlylinked to the group A or through a substituent thereof, rendering themolecule fast to diffusion and corresponding to the formula -Y-D whereinD stands for an acyclic aliphatic hydrocarbon residue with from 5 to 20carbon atoms and Y stands for a chemical bond, oxygen, sulphur,sulphonyl, -N(alkyl)-, -CONH-, -NHCO-, -N(R3)SO2- and -SO2N(R3)- whereinR3 H or alkyl.
 3. A photographic material according to claim 2, whereinA stands for a phenyl nucleus, a thiazolyl nucleus or a pyridyl nucleus.4. A photographic material according to claim 2, wherein A stands forthe group corresponding to the formula : wherein : Y stands for achemical bond, oxygen, sulphur, sulphonyl, -N(alkyl)-, -CONH-, -NHCO-,-N(R3)SO2- and -SO2N(R3)- wherein R3 H or alkyl, D stands for an acyclicaliphatic hydrocarbon residue with from 5 to 20 carbon atoms, Z2 standsfor hydrogen, an alkyl group, an aryl group, a halogen atom, a sulpho orcarboxyl group in acid or salt form, a fluorosulphonyl group, analkoxycarbonyl group, a sulphamoyl group, an alkylsulphonyl group, analkoxy group, an alkylthio group, an aryloxy group, an arylthio group orthe group wherein each of R4 and R5 stands for alkyl, aryl or aralkyl ortogether represent the atoms necessary to form a morpholine orpiperidine nucleus.
 5. Photographic multilayer color material comprisingin one of the light-sensitive silver halide emulsion layers or in anon-light-sensitive water-permeable colloid layer in water-permeablerelationship with the light-sensitive silver halide emulsion layer acolor coupler according to claim
 1. 6. Photographic multilayer colormaterial according to claim 5, comprising three silver halide emulsionlayers which are differently optically sensitized, wherein theblue-sensitive silver halide emulsion layer or a non-light-sensitivecolloid layer in water-permeable relationship therewith incorporates thesaid color coupler.
 7. Process for the production of a photographiccolor image by development of a photographic element containingimage-wise exposed silver halide with the aid of an aromatic primaryamino developing agent, which by reduction of the exposed silver halideis converted into its oxidized form and as such forms a yellowazomethine dye by reaction with a color coupler according to claim
 1. 8.Process according to claim 7, wherein said color coupler is present in ablue-sensitive silver halide emulsion layer or other colloid layer inwater-permeable relationship therewith of the said photographic element.